Halogenovinyl-azole derivatives

ABSTRACT

New halogenovinyl-azole derivatives of the formula ##STR1## in which R 1  represents optionally substituted alkyl, optionally substituted alkenyl, optionally substituted cycloalkyl or optionally substituted aryl, or represents optionally substituted heteroaryl, 
     R 2  represents hydrogen, alkyl, alkenyl, acyl or aralkyl 
     X 1  represents halogen, 
     X 2  represents halogen, 
     X 3  represents hydrogen or halogen 
     Y represents nitrogen or a CH group, 
     and acid addition salts and metal salt complexes thereof 
     are very effective for combating microbes in plant protection and in the preservation of materials.

This is a division of application Ser. No. 384,595 filed Jul. 24, 1989,now U.S. Pat. No. 5,081,140.

The present invention relates to new halogenovinyl-azole derivatives,several processes for their preparation and their use as microbicides inplant protection and in the preservation of materials.

It has already been disclosed that certain hydroxyethylazole derivativescontaining an alkenyl group are suitable for combating fungi (compareEP-OS 0,207,590 and EP-OS 0,257,822). The action of these substances isgood, but leaves something to be desired in some cases when low amountsare applied.

Further, it has already been disclosed that various azolyl derivativescan be used to preserve non-living organic substances against an attackby microorganisms (compare DE-OS (German Published Specification)3,116,607). Thus, for example,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ol and1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pentan-3-olcan be used for the purpose mentioned above. The activity of thesesubstances, however, is not always sufficient in the preservation ofmaterials.

New halogenovinyl-azole derivatives of the formula ##STR2## in which R¹represents optionally substituted alkyl, optionally substituted alkenyl,optionally substituted cycloalkyl or optionally substituted aryl, orrepresents optionally substituted heteroaryl,

R² represents hydrogen, alkyl, alkenyl, acyl or aralkyl

X¹ represents halogen,

X² represents halogen,

X³ represents hydrogen or halogen

Y represents nitrogen or a CH group,

and acid addition salts and metal salt complexes thereof have now beenfound.

The compounds of the formula (I) contain an asymmetrically substitutedcarbon atom and can therefore be obtained in the two optical isomerforms. Depending on the position of the halogen atoms on the doublebond, the substances of the formula (I) can additionally exist in twogeometric isomer forms. The present invention relates both to the isomermixtures and to the individual isomers.

It has furthermore been found that halogenovinyl-azole derivatives ofthe formula (I) and acid addition salts and metal salt complexes thereofare obtained by a process in which

a) alkines of the formula ##STR3## in which R¹, R² and Y have theabovementioned meaning, are reacted with halogen or compounds whichsupply halogen, in the presence of a diluent, or

b) alkenes of the formula ##STR4## in which R¹, R², X¹ and X² have theabovementioned meaning and

Z represents halogen, alkylsulphonate or arylsulphonate,

are reacted with azoles of the formula ##STR5## in which Y has theabovementioned meaning, in the presence of an acid-binding agent and inthe presence of a diluent,

c) alkines of the formula ##STR6## in which R¹, R² and Y have theabovementioned meaning, are reacted, in a first stage, withhypohalogenites of the formula

    MOX.sup.4                                                  (V)

in which

M represents an alkali metal and

X⁴ represents halogen,

in the presence of a diluent, and in a second stage, the halogenoalkinesthus obtained, of the formula ##STR7## in which R¹, R², X⁴ and Y havethe abovementioned meaning, are reacted with halogen or compounds whichsupply halogen, in the presence of a diluent and, if appropriate, anacid or a metal salt is then added onto the compounds of the formula (I)thus obtained.

Finally, it has been found that the new halogenovinyl-azole derivativesof the formula (I) and acid addition salts and metal salt complexesthereof have potent microbicidal properties and can be used in plantprotection as well as in the preservation of materials.

Surprisingly, the substances according to the invention have a betterfungicidal activity in plant protection than the already known compoundsof the same type of action which have the greatest structuralsimilarity.

Further, the compounds according to the invention are also surprisinglybetter suitable for combating undesired microorganisms in thepreservation of materials than1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ol and1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pentan-3-ol,which are structurally similar already known compounds of the same typeof action.

Formula (I) provides a general definition of the halogeno-vinyl-azolederivatives according to the invention. Preferred compounds of theformula (I) are those in which

R¹ represents straight-chain or branched alkyl having 1 to 6 carbonatoms, it being possible for each of these radicals to be substituted byone to three identical or different substituents from the groupcomprising halogen, cycloalkyl having 3 to 7 carbon atoms, phenyl and/orhalogenophenyl, or

R¹ represents alkenyl having 2 to 6 carbon atoms it being possible foreach of these radicals to be substituted by one to three identical ordifferent substituents from the group comprising halogen, phenyl and/orhalogenophenyl, or

R¹ represents cycloalkyl having 3 to 7 carbon atoms, it being possiblefor each of these cycloalkyl radicals to be substituted by one to threeidentical or different substituents from the group comprising halogenand/or alkyl having 1 to 4 carbon atoms, or

R¹ represents phenyl, which can be substituted by one to three identicalor different substituents from the group comprising halogen, alkylhaving 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthiohaving 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or2 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 to 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy part,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy part and 1 to 4carbon atoms in the alkyl part, nitro and/or cyano, or

R¹ represents an optionally benzo-fused five- or six-memberedheteroaromatic radical having 1 to 3 heteroatoms, such as nitrogen,sulphur and/or oxygen, it being possible for each of these radicals tobe substituted by one to three identical or different substituents fromthe group comprising halogen, alkyl having 1 to 4 carbon atoms,hydroxyalkyl having 1 to 4 carbon atoms, hydroxyalkinyl having 3 to 8carbon atoms, alkoxy having 1 to 2 carbon atoms, alkylthio having 1 or 2carbon atoms, halogenoalkyl, halogenoalkoxy and halogenoalkylthio havingin each case 1 or 2 carbon atoms and 1 to 5 identical or differenthalogen atoms, such as fluorine or chlorine atoms, formyl,dialkoxymethyl having 1 or 2 carbon atoms in each alkoxy group, acylhaving 2 to 4 carbon atoms, alkoxycarbonyl having 1 to 4 carbon atoms inthe alkoxy part, alkoximinoalkyl having 1 to 4 carbon atoms in thealkoxy part and 1 to 3 carbon atoms in the alkyl part, nitro and/orcyano,

R² represents hydrogen, alkyl having 1 to 6 carbon atoms, alkenyl having3 to 6 carbon atoms, acyl having 1 to 4 carbon atoms or phenylalkylhaving 1 to 4 carbon atoms in the alkyl part,

X¹ represents fluorine, chlorine, bromine or iodine,

X² represents fluorine, chlorine, bromine or iodine,

X³ represents hydrogen, chlorine, bromine or iodine and

Y represents a nitrogen atom or a CH group.

Particularly preferred compounds of the formula (I) are those in which

R¹ represents methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-butyl,tert.-pentyl, 1-ethyl-1-methyl-propyl, 1,1-dimethyl-pentyl,1,1,2-trimethylpropyl or 1,1-dimethyl-prop-2-enyl, it being possible foreach of these abovementioned radicals to be substituted by one to threeidentical or different substituents from the group comprising fluorine,chlorine, bromine, phenyl, chlorophenyl, dichlorophenyl, fluorophenyland/or difluorophenyl, or

R¹ represents 1-methyl-cyclohexyl, cyclohexyl, 1-chloro-cyclopropyl,1-methyl-cyclopropyl, cyclopropyl, 1-methyl-cyclopentyl, cyclopentyl or1-ethyl-cyclopentyl, or represents phenyl, which can be substituted byone to three identical or different substituents from the groupcomprising fluorine, chlorine, bromine, methyl, ethyl, tert.-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluoromethoxy, chlorofluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinoethyl, 1-methoximinoethyl,nitro and/or cyano, or

R¹ represents pyrazolyl, imidazolyl, 1,2,4-triazolyl, pyrrolyl, furanyl,thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl,quinolinyl, isoquinolinyl, quinazolinyl, indolyl, benzothienyl,benzofuranyl, benzothiazolyl or benzimidazolyl, it being possible foreach of these radicals to be substituted by one to three identical ordifferent substituents from the group comprising fluorine, chlorine,bromine, methyl, ethyl, tert.-butyl, methoxy, ethoxy, methylthio,trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, chlorodifluoromethylthio, hydroxymethyl,hydroxyethyl, hydroxyalkinyl having 4 to 6 carbon atoms,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximino-ethyl,nitro, cyano, formyl, dimethoxymethyl, acetyl and/or propionyl,

R² represents hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl,allyl, formyl, acetyl, benzyl or phenethyl,

X¹ represents fluorine, chlorine, bromine or iodine,

X² represents fluorine, chlorine, bromine or iodine, and

X³ represents hydrogen, chlorine, bromine or iodine, and

Y represents a nitrogen atom or a CH group.

Addition products of acids and those halogenovinyl-azole derivatives ofthe formula (I) in which R¹, R², X¹, X², X³ and Y have those meaningswhich have been mentioned as preferred for these substituents are alsopreferred compounds according to the invention.

The acids which can be added on include, preferably, hydrogen halideacids, such as, for example, hydrochloric acid and hydrobromic acid, inparticular hydrochloric acid, and furthermore phosphoric acid, nitricacid, mono- and bifunctional carboxylic acids and hydroxycarboxylicacids, such as, for example, acetic acid, maleic acid, succinic acid,fumaric acid, tartaric acid, citric acid, salicyclic acid, sorbic acidand lactic acid, and sulphonic acids, such as, for example,p-toluenesulphonic acid and 1,5-naphthalenedisulphonic acid.

Addition products of salts of metals of main groups II to IV and ofsub-groups I and II and IV to VIII of the periodic table of the elementsand those halogenovinyl-azole derivatives of the formula (I) in whichR¹, R², X¹, X², X³ and Y have those meanings which have been mentionedas preferred for these substituents are furthermore preferred compoundsaccording to the invention.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel areparticularly preferred here. Possible anions of these salts are thosewhich are derived from those acids which lead to physiologicallytolerated addition products. Particularly preferred acids of this typein this context are the hydrogen halide acids, such as, for example,hydrochloric acid and hydrobromic acid, and furthermore phosphoric acid,nitric acid and sulphuric acid.

Examples of suitable substances according to the invention are thehalogenovinyl-azole derivatives listed in the following table.

                                      TABLE 1                                     __________________________________________________________________________     ##STR8##                                                                     X.sup.1                                                                          X.sup.2                                                                         X.sup.3                                                                          R.sup.1        R.sup.2    Y                                           __________________________________________________________________________    I  I H  C(CH.sub.3).sub.3                                                                            H          N                                           F  F H  C(CH.sub.3).sub.3                                                                            H          N                                           I  I H  C(CH.sub.3).sub.3                                                                            H          CH                                          F  F H  C(CH.sub.3).sub.3                                                                            H          CH                                          Cl Cl                                                                              H  C(CH.sub.3).sub.3                                                                            CH.sub.3   N                                           Cl Cl                                                                              H  C(CH.sub.3).sub.3                                                                            C.sub.2 H.sub.5                                                                          N                                           Br Br                                                                              H  C(CH.sub.3).sub.3                                                                             ##STR9##  N                                           Cl Cl                                                                              H  C(CH.sub.3).sub.3                                                                             ##STR10## N                                           Cl Cl                                                                              H                                                                                 ##STR11##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR12##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR13##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR14##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR15##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR16##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR17##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR18##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR19##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR20##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR21##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR22##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR23##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR24##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR25##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR26##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR27##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR28##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR29##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR30##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR31##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR32##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR33##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR34##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR35##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR36##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR37##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR38##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR39##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR40##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR41##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR42##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR43##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR44##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR45##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR46##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR47##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR48##     H          N                                           Cl Cl                                                                              H                                                                                 ##STR49##     H          N                                           Cl Cl                                                                              Cl C(CH.sub.3).sub.3                                                                            CH.sub.3   N                                           Cl Br                                                                              Br C(CH.sub.3).sub.3                                                                            CH.sub.3   N                                           Cl Cl                                                                              Cl                                                                                ##STR50##     H          N                                           Cl Br                                                                              Br                                                                                ##STR51##     H          N                                           Cl Cl                                                                              Cl                                                                                ##STR52##     H          N                                           Cl Cl                                                                              Cl                                                                                ##STR53##     H          N                                           Cl Cl                                                                              Cl                                                                                ##STR54##     H          N                                           __________________________________________________________________________

If 4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-pent-1-ine isused as the starting substance and chlorine gas is used as the reactioncomponent, the course of process (a) according to the invention can beillustrated by the following equation: ##STR55##

If 1,2-dichloro-3-hydroxy-3-chloromethyl-4,4-dimethyl-pent-1-ene and1,2,4-triazole are used as starting substances, the course of process(b) according to the invention can be illustrated by the followingequation: ##STR56##

If 4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-pent-1-ine isused as the starting substance and sodium hypochlorite as well asbromine are used as reaction components, the course of process (c)according to the invention can be illustrated by the following equation:##STR57##

Formula (II) provides a general definition of the alkines required asstarting substances in carrying out process (a) according to theinvention. In this formula, R¹, R² and Y preferably have those meaningswhich have already been mentioned as preferred for these radicals inconnection with the description of the substances of the formula (I)according to the invention.

The alkines of the formula (II) have not previously been disclosed. Theycan be prepared by a process in which

d) azolyl-methyl-ketones of the formula ##STR58## in which R¹ and Y havethe abovementioned meaning, are reacted with acetylene salts of theformula

    HC.tbd.CMe                                                 (VIII)

in which Me represents an equivalent of a metal cation, in the presenceof a diluent, and if appropriate the alkines formed in this reaction ofthe formula ##STR59## in which R¹ and Y have the abovementioned meaning,are reacted with strong bases in the presence of a diluent, and thealcoholates formed in this reaction of the formula ##STR60## in which R¹and Y have the abovementioned meaning and

R³ represents a cationic radical of a base,

are reacted with halogen compounds of the formula

    R.sup.4 --Hal                                              (IX)

in which

R⁴ represents alkyl, alkenyl, acyl or aralkyl and

Hal represents chlorine, bromine or iodine,

in the presence of a diluent, or

e) chloromethyl ketones of the formula ##STR61## in which R¹ has theabovementioned meaning, are reacted with acetylenes of the formula

    HC.tbd.CR.sup.5                                            (XI)

in which R⁵ represents hydrogen or an equivalent of a metal cation, ifappropriate in the presence of a base and in the presence of a diluent,and the hydroxyalkines formed in this reaction, of the formula ##STR62##in which R¹ has the abovementioned meaning, are then reacted with azolesof the formula ##STR63## in which Y has the abovementioned meaning, inthe presence of an acid-binding agent and in the presence of a diluent,and if appropriate the alkines formed in this reaction of the formula##STR64## in which R¹ and Y have the abovementioned meaning, are furtherreacted in accordance with process (d).

Formula (VII) provides a general definition of the azolyl-methyl ketonesrequired as starting substances in carrying out process (d). In thisformula, Y and R¹ preferably have those meanings which have already beenmentioned as preferred for these radicals in connection with thedescription of the substances of the formula (I) according to theinvention.

The azolyl-methyl ketones of the formula (VII) are known or can beprepared in a simple manner by processes which are known in principle(compare DE-OS (German Published Specification) 2,431,407).

Formula (VII) provides a general definition of the acetylene saltsrequired as reaction components in process (d). In this formula, Mepreferably represents a lithium cation or one equivalent of acerium(III) cation.

The acetylene salts of the formula (VIII) are known (compareHouben-Weyl, "Methoden der Organischen Chemie (Methods of OrganicChemistry)", Volume V/2a, pages 509 et seq., Georg Thieme Verlag,Stuttgart 1977 and Tetrahedron Letters 25, (1984) 4233).

Diluents which can be used for carrying out the first stage of process(d) are all the inert organic solvents customary for such reactions.Preferred possible solvents are ethers, such as tetrahydrofuran ordiethyl ether, and in addition hydrocarbons, such as n-hexane.

The reaction temperatures can be varied within a substantial range incarrying out the first stage of process (d). The reaction is in generalcarried out at temperatures between -78° C. and +30° C., preferably attemperatures between -70° C. and +20° C.

In carrying out process (d), as when carrying out processes (a), (b),(c) and (e), normal pressure is in general applied.

In carrying out the first stage of process (d), a procedure is ingeneral followed in which first the acetylene salts are prepared andthese are then reacted, without prior isolation, with an equivalentamount or an excess or less than the equivalent amount of azolyl-methylketone of the formula (VII). Working up is carried out by customarymethods. In general, a procedure is followed in which an aqueous saltsolution, for example ammonium chloride solution, is first added to thereaction mixture, the reaction mixture is then extracted several timeswith an organic solvent of low water-solubility and the combined organicphases are dried under reduced pressure and concentrated.

In carrying out the second stage of process (d), the conversion of thealkines of the formula (IIa) into the corresponding alcoholates iscarried out by reaction with suitable strong bases, such as alkali metalamides or hydrides, quaternary ammonium hydroxides or phosphoniumhydroxides, in an inert diluent, such as, for example, dioxane, at roomtemperature. Accordingly, R³ in the compounds of the formula (IIb)preferably represents an alkali metal cation, such as a sodium orpotassium cation, or a quaternary ammonium or phosphonium cation.

Formula (IX) provides a general definition of the halogen compoundsrequired as reaction components in carrying out the third stage ofprocess (d). In this formula, R⁴ preferably represents the meaningswhich have already been mentioned for the substituent R² in connectionwith the description of the substances of the formula (I) according tothe invention, with the exception of the meaning of hydrogen. Halrepresents chlorine, bromine or iodine.

The halogen compounds of the formula (IX) are known or can be preparedby methods which are known in principle.

Possible diluents in carrying out the second and third stage of process(d) are inert organic solvents. Solvents which can preferably be usedare ethers, such as diethyl ether or dioxane; aromatic hydrocarbons,such as benzene, and in individual cases also chlorinated hydrocarbons,such as chloroform, methylene chloride or carbon tetrachloride, as wellas hexamethylphosphoric triamide.

The reaction temperatures can be varied within a substantial range incarrying out the second and third stage of process (d). The reaction isin general carried out at temperatures between 0° C. and 120° C.,preferably between 20° C. and 100° C.

In carrying out the second stage of process (d), alkines of the formula(IIa) are first reacted with strong bases to give the correspondingalcoholates of the formula (IIb). In the subsequent third stage, 1 to 2mol of halogen compound of the formula (IX) are preferably employed permole of an alcoholate of the formula (IIb). To isolate the end products,the reaction mixture is freed from the solvent, and water and an organicsolvent are added to the residue. The organic phase is separated off,worked up in the customary manner and purified.

In a preferred embodiment, the procedure in the second and third stageof process (d) is advantageously such that a hydroxy compound of theformula (IIa) is used as the starting substance, the latter is convertedinto the alkali metal alcoholate in a suitable organic solvent by meansof an alkali metal hydride or alkali metal amide, and the product isimmediately reacted, without being isolated, with a halogen compound ofthe formula (IX), alkali metal halide being eliminated to give thecompounds of the formula (II) in one operation.

According to another preferred embodiment, the preparation of thealcoholates and the reaction with a halogen compound of the formula (IX)are advantageously carried out in a two-phase system, such as, forexample, aqueous sodium hydroxide solution or potassium hydroxidesolution/toluene or methylene chloride, with the addition of 0.01-1 molof a phase transfer catalyst, such as, for example, ammonium compoundsor phosphonium compounds, the alcoholates being reacted in the organicphase in the organic phase or at the interface with the halidescontained.

Formula (X) provides a general definition of the chloromethyl ketonesrequired as starting substances in carrying out process (e). In thisformula, R¹ preferably has those meanings which have already beenmentioned as preferred for this radical in connection with thedescription of the substances of the formula (I) according to theinvention.

The chloromethyl ketones of the formula (X) are known or can be preparedby methods which are known in principle (compare DE-OS (German PublishedSpecification) 3,049,461).

Formula (XI) provides a general definition of the acetylenes required asreaction components in process (e). In this formula, R⁵ preferablyrepresents hydrogen, a lithium cation or one equivalent of a magnesiumor cerium(III) cation.

The acetylenes of the formula (XI) are known.

Possible bases in carrying out the first stage of process (e) are allthe strong bases which are customary for such reactions. Bases which canpreferably be used are alkali metal hydroxides, such as potassiumhydroxide.

All the inert organic solvents customary for such reactions can be usedas diluents in carrying out the first stage of process (e). Preferredpossible solvents are ethers, such as tetrahydrofuran or diethyl ether.

The reaction temperatures can be varied within a substantial range incarrying out the first stage of process (e). The reaction is in generalcarried out at temperatures between -78° C. and +50° C., preferablybetween -78° C. and +40° C.

In carrying out the first stage of process (e), a procedure is ingeneral followed in which chloromethyl ketones of the formula (X) andacetylenes of the formula (XI) are reacted in approximately equivalentamounts. However, it is also possible to use one or the other of thecomponents in excess. Working up is carried out by customary methods.The hydroxyalkines of the formula (XII) can be further reacted directlywith azoles of the formula (IV). However, they can also first beconverted into oxiranes and these can then be reacted with azoles of theformula (IV).

In carrying out the second stage of process (e), possible acid-bindingagents are all the customary acid acceptors. Acid acceptors which canpreferably be used are alkali metal carbonates and bicarbonates, such assodium carbonate, potassium carbonate or sodium bicarbonate, andfurthermore tertiary aliphatic or aromatic amines, such astriethylamine, N,N-dimethyl-cyclohexyl-amine, N,N-dimethyl-benzylamineand pyridine, and also cyclic amines, such as1,5-diaza-bicyclo[4.3.0]non-5-ene (DBN),1,8-diaza-bicyclo[5.4.0]undec-7-ene (DBU) and1,4-diaza-bicyclo[2.2.2]octane (DABCO).

Possible diluents in carrying out the second stage of process (e) areall the inert organic solvents. Solvents which can preferably be usedare aliphatic and aromatic optionally halogenated hydrocarbons, such aspentane, hexane, cyclohexane, petroleum ether, benzine, ligroin,benzene, toluene, xylene, methylene chloride, ethylene chloride,chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene,ethers, such as dimethyl ether, dibutyl ether, tert.-butyl methyl ether,glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran anddioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropylketone and methyl isobutyl ketone, esters, such as methyl and ethylacetate, nitriles, such as, for example, acetonitrile and propionitrile,and pyridine.

The reaction temperatures can also be varied within a substantial rangein carrying out the second stage of process (e). The reaction is ingeneral carried out at temperatures between 0° C. and 200° C.,preferably between 20° C. and 150° C.

In carrying out the second stage of process (e), a procedure is ingeneral followed in which an equivalent amount or even an excess ofazole of the formula (IV) and 2 to 3 mol of acid-binding agent areemployed per mole of hydroxyalkine of the formula (XII). Working up iscarried out by customary methods. Further reaction of the alkines of theformula (IIa) which may be desired is carried out in process (e) in thesame manner as in process (d).

Preferred possible halogens as reaction components in carrying outprocess (a) according to the invention are fluorine, chlorine, bromineand iodine, and furthermore mixed halogens, such as chlorine(I)fluoride, bromine(I) fluoride, iodine(I) fluoride, bromine(I) chloride,iodine(I) chloride or iodine(I) bromide (see Methodicium Chimicium, F.Korte, Volume 7, page 842 (1976).

Examples of compounds which supply halogen which may be used aresulphuryl chloride, N-bromosuccinimide with hydrochloric acid,N-chlorosuccinimide with hydrobromic acid or N-chlorosuccinimide withhydrofluoric acid/pyridine (see Synthesis 1973, 780).

The addition of the halogens onto the alkines of the formula (II) can bepromoted by the action of light, by heat, by substances which form freeradicals, such as organic peroxides, or by surface-active substances,such as charcoal, or metal salts, such as copper(II) chloride oriron(III) chloride. The isomer ratio (E/Z) can in some cases beinfluenced in this way (see Houben-Weyl, Methoden der Org. Chemie(Methods of Organic Chemistry), Volume V/3, page 551 (1962)).

Diluents which can be used in carrying out process (a) according to theinvention are all the inert organic solvents customary for suchreactions. Solvents which can preferably be used are halogenatedaliphatic hydrocarbons, such as methylene chloride, chloroform andcarbon tetrachloride.

The temperatures can be varied within a certain range in carrying outprocess (a) according to the invention. In general, the reaction iscarried out at temperatures between -10° C. and +120° C., preferablybetween -5° C. and +80° C.

In carrying out process (a) according to the invention, in general anequivalent amount or an excess of halogen or halogen-supplying compoundis employed per mole of alkine of the formula (II). Working up iscarried out by customary methods. In general, a procedure is followed inwhich the mixture is diluted with an organic solvent of lowwater-solubility, washed with water, and the organic phase is dried andconcentrated. However, it is also possible for the reaction mixture tobe concentrated directly, when the reaction has ended, by stripping offthe volatile components under reduced pressure. If appropriate, theproducts formed can be further purified by customary methods.

Formula (III) provides a general definition of the alkenes required asstarting substances in process (b) according to the invention. In thisformula, R¹, R², X¹ and X² preferably have those meanings which, inconnection with the description of the substances of the formula (I)according to the invention, have already been mentioned as preferred forthese substances. Z preferably represents chlorine, bromine, iodine,methylsulphonate or p-tolylsulphonate.

The alkenes of the formula (III) can be prepared by customary methods.Thus, for example, alkenes of the formula (III) are obtained by reactinghydroxyalkines of the formula (XII) with halogens in the presence of adiluent. The reaction conditions used correspond to those used in thecase of process (a) according to the invention.

Possible diluents in carrying out process (b) according to the inventionare all the customary inert organic solvents. Those solvents which havealready been mentioned as preferred solvents in connection with thedescription of the second stage of process (e) can preferably be used.

Possible acid-binding agents in carrying out process (b) according tothe invention are all the customary acid acceptors. All thoseacid-binding agents which have already been mentioned as preferred acidacceptors in connection with the description of the second stage ofprocess (e) can preferably be used.

The reaction temperatures can be varied within a substantial range incarrying out process (b) according to the invention. The reaction is ingeneral carried out at temperatures between 0° C. and 150° C.,preferably between 20° C. and 120° C.

In carrying out process (b) according to the invention, a procedure isin general followed in which an equivalent amount or an excess of azoleof the formula (IV) and 2 to 3 mol of acid-binding agent are employedper mole of alkene of the formula (III). Working up is carried out bycustomary methods.

Formula (V) provides a general definition of the hypohalogenitesrequired as reaction components in carrying out process (c) according tothe invention. In this formula, M preferably represents a sodium orpotassium ion, and X⁴ preferably represents chlorine, bromine andiodine.

Possible diluents in carrying out the first stage as well as the secondstage of process (c) according to the invention are all inert organicsolvents which are customarily used for reactions of this type. Solventswhich can preferably be used are halogenated aliphatic hydrocarbons,such as methylene chloride, chloroform and carbon tetrachloride.

The reaction temperatures can be varied within a certain range incarrying out the first stage as well as the second stage of process (c)according to the invention. In general, the reaction is carried out attemperatures between -10° C. and +120° C., preferably between -5° C. and+80° C.

In carrying out the first stage of process (c) according to theinvention, in general an excess of hypohalogenite is employed per moleof alkine of the formula (II).

In carrying out the second stage of process (c) according to theinvention, in general an equivalent amount or an excess of halogen orhalogen-supplying compound is employed per mole of halogeno-alkine ofthe formula (VI). In carrying out the first stage as well as the secondstage, working up is carried out by customary methods.

The halogenovinyl-azole derivatives of the formula (I) obtainable by theprocesses according to the invention can be converted into acid additionsalts or metal salt complexes.

Those acids which have already been mentioned as preferred acids inconnection with the description of the acid addition salts according tothe invention are preferably suitable for the preparation of acidaddition salts of the compounds of the formula (I).

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary salt formation methods, forexample by dissolving a compound of the formula (I) in a suitable inertsolvent and adding the acid, for example hydrochloric acid, and they canbe isolated in a known manner, for example by filtration, and ifappropriate purified by washing with an inert organic solvent.

Those salts of metals which have already been mentioned as preferredmetal salts in connection with the description of the metal saltcomplexes according to the invention are preferably suitable for thepreparation of metal salt complexes of the compounds of the formula (I).

The metal salt complexes of the compounds of the formula (I) can beobtained in a simple manner by customary processes, such as, forexample, by dissolving the metal salt in alcohol, for example ethanol,and adding the solution to compounds of the formula (I). The metal saltcomplexes can be isolated in a known manner, for example by filtration,and, if appropriate, purified by recrystallization.

The active compounds according to the invention have potent microbicidalaction and can be used as fungicides in plant protection and in thepreservation of materials.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above may be mentioned as examples, butnot by way of limitation:

Xanthomonas species, such as, for example, Xanthomonas oryzae;Pseudomonas species, such as, for example, Pseudomonas lachrymans;Erwinia species, such as, for example, Erwinia amylovora; Pythiumspecies, such as, for example, Pythium ultimum; Phytophthora species,such as, for example, Phytophthora infestans; Pseudoperonospora species,such as, for example, Pseudoperonospora humuli or Pseudoperonosporacubensis; Plasmopara species, such as, for example, Plasmopara viticola;Peronospora species, such as, for example, Peronospora pisi or P.brassicae; Erysiphe species, such as, for example, Erysiphe graminis;Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;Podosphaera species, such as, for example, Podosphaera leucotricha;Venturia species, such as, for example, Venturia inaequalis; Pyrenophoraspecies, such as, for example, Pyrenophora teres or P. graminea (conidiaform: Drechslera, syn: Helminthosporium); Cochliobolus species, such as,for example, Cochliobolus sativus (conidia form: Drechslera, syn:Helminthosporium); Uromyces species, such as, for example, Uromycesappendiculatus; Puccinia species, such as, for example, Pucciniarecondita; Tilletia species, such as, for example, Tilletia caries;Ustilago species, such as, for example, Ustilago nuda or Ustilageavenae; Pellicularia species, such as, for example, Pelliculariasasakii; Pyricularia species, such as, for example, Pyricularia oryzae;Fusarium species, such as, for example, Fusarium culmorum; Botrytisspecies, such as, for example, Botrytis cinerea; Septoria species, suchas, for example, Septoria nodorum; Leptosphaeria species, such as, forexample, Leptosphaeria nodorum; Cercospora species, such as, forexample, Cercospora canescens; Alternaria species, such as, for example,Alternaria brassicae and Pseudocercosporella species, such as, forexample, Pseudocercosporella herpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compounds according to the invention are particularlysuitable for combating cereal and rice diseases, such asPseudocercosporella, Erysiphe, Fusarium, Pyrenophora, Cochliobolus,Pyricularia and Pellicularia, and for combating cucumber mildew andapple scab, and also for combating Botrytis in fruit, wine and vegetablegrowing.

In the preservation of materials, the compounds according to theinvention can be used to preserve industrial materials against attack ordestruction by undesired microorganisms. Industrial materials in thisconnection are to be understood as non-living materials which have beenprepared for use in industry. Industrial materials which are to beprotected from microbial change or destruction by the active compoundsaccording to the invention can be, for example, adhesives, sizes, paper,card, textiles, leather, wood, paints, articles made of plastic, coolinglubricants and other materials which can be attacked or decomposed bymicroorganisms. In the context of the materials to be preserved,components of production lines, for example cooling water circulations,which can be impaired by multiplication of microorganisms may also bementioned. Industrial materials which may be mentioned as preferred inthe context of the present invention are adhesives, sizes, paper andcard, leather, wood, paints, cooling lubricants and coolingcirculations, particularly preferably wood.

Examples which may be mentioned of microorganisms which can causedegradation to or a change in the industrial materials are bacteria,fungi, yeasts, algae and slime organisms. The active compounds accordingto the invention preferentially act against fungi, in particular moulds,fungi which discolour and destroy wood (Basidiomycetes), and againstslime organisms and algae.

Microorganisms of the following genera may be mentioned as examples:Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillusniger, Chaetomium, such as Chaetomium globosum, Coniophora, such asConiophora puteana, Lentinus, such as Lentinus tigrinus, Penicillium,such as Penicillium glaucum, Polyporus, such as Polyporus versicolor,Aureobasidium such as Aureobasidium pullulans, Sclerophoma, such asSclerophoma pityophila, Trichoderma, such as Trichoderma viride,Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonasaeruginosa and Staphylococcus, such as Staphylococcus aureus.

The substances according to the invention moreover also have plantgrowth-regulating properties.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted to the customary formulations, such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, very fine capsules in polymeric substances and in coatingcompositions for seed, as well as ULV cold mist and warm mistformulations.

The formulations are produced in known manner, for example by mixing theactive compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-dispersed silicic acid, alumina and silicates;as solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, maize cobs and tobacco stalks; as emulsifying and/orfoam-forming agents there are suitable: for example non-ionic andanionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products; as dispersing agents there are suitable:for example ligninsulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

If applied in plant protection, the formulations in general containbetween 0.1 and 95 per cent by weight of active compound, preferablybetween 0.5 and 90%.

If applied in plant protection, the active compounds according to theinvention can be present in the formulations as a mixture with otherknown active compounds, such as fungicides, insecticides, acaricides andherbicides, and in mixtures with fertilizers and growth regulators.

If applied in plant protection, the active compounds can be used as suchor in the form of their formulations or the use forms preparedtherefrom, such as ready-to-use solutions, suspensions, wettablepowders, pastes, soluble powders, dusts and granules. They are used inthe customary manner, for example by watering, spraying, atomizing,scattering, dusting, foaming, brushing on and the like. It isfurthermore possible to apply the active compounds by the ultra-lowvolume method or to inject the active compound formulation or the activecompound itself into the soil. The seed of the plants can also betreated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02% by weight, are required atthe place of action.

Microbicidal agents in general contain the active compounds in an amountof 1 to 95% by weight, preferably 10 to 75% by weight.

In the preservation of materials, the use concentrations of the activecompounds according to the invention depend on the nature and occurrenceof the microorganisms to be combated and on the composition of thematerial to be preserved. The optimum amount to be used can bedetermined by test series. The use concentrations are in general in therange from 0.001 to 5% by weight, preferably 0.05 to 1.0% by weight,based on the material to be preserved.

In the preservation of materials, the active compounds according to theinvention can also be used in mixture with other known active compounds.The following active compounds may be mentioned as examples: benzylalcohol mono(poly)hemiformal and other compounds which split offformaldehyde, benzimidazolyl methylcarbamates, tetramethylthiuramdisulphide, zinc salts of dialkyldithiocarbamates,2,4,5,6-tetrachloroisophthalonitrile, thiazolylbenzimidazole,mercaptobenzothiazole, organotin compounds, methylene bisthiocyanate,2-thiocyanatomethylthiobenzothiazole, phenol derivatives, such as2-phenylphenol, (2,2'-di-hydroxy-5,5'-dichloro)diphenylmethane and3-methyl-4-chlorophenol, N-trihalogenomethylthio compounds, such asfolpet, fluorofolpet, dichlofluanid.

The preparation and use of the active compounds according to theinvention are illustrated by the following examples.

PREPARATION EXAMPLES Example 1 ##STR65##

A stream of chlorine gas is passed into a solution of 3.86 g (20 mmol)of 4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)methyl]-1-pentine in 20ml of absolute methylene chloride at 0° to 5° C. over a period of 6hours, while irradiating with a 500 watt lamp. The reaction mixture issubsequently stirred at room temperature for 15 hours and then dilutedwith methylene chloride and extracted by shaking with water. The organicphase is dried and then concentrated under reduced pressure by strippingoff the solvent. 4.7 g (89% of theory) of1,2-dichloro-4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-1-penteneare obtained in the form of a solid substance of melting point 49°-52°C. This substance is a mixture of isomers A:B=1:50.

NMR (CDCl₃): (B) δ1.15 (s, 9H) 4.3 (d, J=14 Hz, 1H), 5.0 (d, J=14 Hz,1H), 6.68 (s, 1H), 7.95 (s, 1H), 8.25 (s, 1H)

Preparation of the Starting Substance ##STR66##

13 g (0.5 mol) of acetylene are passed into 880 ml of absolutetetrahydrofuran at -70° C. and metalated by dropwise addition of 200 ml(0.5 mol) of butyllithium in hexane. After 30 minutes, a solution of78.5 g (0.47 mol) of 3,3-dimethyl-1-(1,2,4-triazol-1-yl)-2-butanone in150 ml of absolute tetrahydrofuran is added dropwise at -70° C. Thereaction mixture is subsequently stirred at -70° C. for 2 hours and thenthawed and stirred at 20° C. for a further 2 hours. After dilution withsaturated aqueous ammonium chloride solution, the mixture is extractedseveral times by shaking with methylene chloride. The combined organicphases are dried and then concentrated under reduced pressure. 74 g of aproduct which, according to analysis by gas chromatography, consists of38% of 3,3-dimethyl-1-(1,2,4-triazol-1-yl)-2-butanone and of 57% of4,4-dimethyl- 3-hydroxy-3-[(1,2,4-triazol-1-yl)methyl]-1-pentine remain.After recrystallization from toluene, pure4,4-dimethyl-3-hydroxy-[(1,2,4-triazol-1-yl)-methyl]-1-pentine ofmelting point 129°-131° C. is obtained.

NMR (CDCl₃): δ1.2 (s, 9H), 2.35 (s, 1H), 3.75 (OH), 4.4 (AB, 2H), 8.0(s, 1H), 8.25 (s, 1H).

Example 2 ##STR67##

25 g of charcoal are initially introduced in granule form into 100 ml ofabsolute methylene chloride at 0°-5° C. 6.3 g (88 mmol) of chlorine gasare then passed in, 9.65 g (50 mmol) of4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-1-pentine in 100ml of absolute methylene chloride are then added dropwise and themixture is subsequently stirred at room temperature for 13 hours. Afterfiltering and stripping off the solvent, 3.2 g of1,2-dichloro-4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-1-pentaneremain as a mixture of isomers A:B=25:1 of melting point 59°-62° C.

NMR (CDCl₃): δ1.2 (s, 9H), 2.85 (OH), 4.3 (broad t, 1H), 5.0 (broad t,1H), 6.35 (s, 1H), 8.05 (s, 1H), 8.4 (broad s, 1H)

Example 3 ##STR68##

A solution of 6.4 g (40 mmol) of bromine in 20 ml of methylene chlorideis added dropwise to a solution of 3.86 g (20 mmol) of4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-1-pentine in 30ml of absolute methylene chloride at 0° to 5° C., while stirring. Thereaction mixture is subsequently stirred at 20° C. for 5 hours and thenconcentrated by stripping off volatile constituents under reducedpressure. 5.7 g (81% of theory) of1,2-dibromo-4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-1-penteneare obtained in this manner in the form of an oil. This substance is amixture of isomers A:B=1:25.

NMR (CDCl₃): (B) δ1.25 (s, 9H), 4.4 (d, J=15 Hz, 1H), 5.1 (d, J=15 Hz,1H), 6.7 (s, 1H), 8.2 (s, 1H), 8.9 (s, 1H).

EXAMPLE 4 ##STR69##

Hydrogen chloride gas is passed into a solution of 1.93 g (10 mmol) of4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-1-pentine in 30ml of methylene chloride at -20° C. until saturation is reached. 1.8 g(20 mmol) of N-bromosuccinimide are then added in portions and themixture is subsequently stirred at 0° C. for 1 hour and at roomtemperature for 12 hours. HCl and solvent are stripped off in vacuo andthe residue is worked up with methylene chloride and dilute sodiumhydroxide solution. 2.1 g (68% of theory) of1-bromo-2-chloro-4,4-dimethyl-3-hydroxy-3-((1,2,4-triazol-1-yl)-methyl]-1-penteneare thus obtained as a mixture of isomers of melting point 45°-48° C.

The compounds listed in the following table 2 are also prepared by themethods described in Examples 1 to 4:

                                      TABLE 2                                     __________________________________________________________________________     ##STR70##                                                                    Example                                                                            Compound                      Melting                                    No.  No.   X.sup.1                                                                         X.sup.2                                                                         R.sup.1     R.sup.2                                                                            Y  point (°C.)                         __________________________________________________________________________     5   I-5   Cl                                                                              Cl                                                                               ##STR71##  H    N  151-152 (Isomeric mixture)                  6   I-6   Br                                                                              Br                                                                               ##STR72##  H    N  95 (decomposition) (Isomeric mixture)       7   I-7   Br                                                                              Br                                                                               ##STR73##  H    N  118-122 (Isomeric mixture)                  8   I-8   Cl                                                                              Cl                                                                               ##STR74##  H    N  135-160 (Isomeric mixture)                  9   I-9   Cl                                                                              Cl                                                                              C(CH.sub.3).sub.3                                                                         CH.sub.3                                                                           N  Oil                                        10   I-10  Cl                                                                              Cl                                                                              C(CH.sub.3).sub.3                                                                         COCH.sub.3                                                                         N  87-92                                      11   I-11  Cl                                                                              Cl                                                                               ##STR75##  H    N  Oil                                        12   I-12  Cl                                                                              Cl                                                                               ##STR76##  H    N  Oil                                        13   I-13  Br                                                                              Br                                                                               ##STR77##  H    CH Oil                                        14   I-14  Br                                                                              Br                                                                               ##STR78##  H    N  Oil                                        15   I-15  Br                                                                              Br                                                                               ##STR79##  H    N  154-158                                    16   I-16  Cl                                                                              Cl                                                                              C(CH.sub.3).sub.3                                                                         H    N  53-56                                                                         (Isomeric                                                                     mixture)                                   __________________________________________________________________________

EXAMPLE 17 ##STR80##

9.65 (50 mmol) of4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-1-pentine in 20ml of methylene chloride are stirred for 3 days with 400 ml (150 mmol)of a solution of sodium hypochlorite at room temperature. The reactionmixture is then extracted by shaking with methylene chloride. Afterdrying the organic phase and stripping off the solvent in vacuo, thereare obtained 9.8 g (43 mmol; 86% of theory) of1-chloro-4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-1-pentinehaving a melting point of 88° C.

NMR (CDCl₃): δ1.15 (s, 3H), 4.4 (s, 2H) 8.0 (s, 1H), 8.3 (s, 1H)

1.6 g of bromine dissolved in 10 ml of absolute methylene chloride areadded dropwise to a solution of 2,3 g (10 mmol) of1-chloro-4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-1-pentinein 20 ml of absolute methylene chloride at 20° C. The reaction mixtureis subsequently stirred for 5 hours at room temperature and then thesolvent is stripped off under reduced pressure. 3.8 g (100% of theory)of1-chloro-1,2-dibromo-4,4-dimethyl-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methyl]-1-penteneare obtained in the form of a solid substance of melting point 78°-81°C. This substance is a mixture of isomers A:B=1:3,6

NMR (CDCl₃): A) δ1.25 (s, 9H), 4.4 (d, J=14 Hz, 1H) 5.25 (d, J=14 Hz,1H), 5.6 (OH), 8.1 (s, 1H), 8.7 (s, 1H). B) δ1.25 (s, 9H), 4.6 (d, J=14Hz, 1H) 5.2 (d, J=14 Hz, 1H), 5.6 (OH), 8.1 (s, 1H), 8.9 (s, 1H).

The compounds listed in the following table 3 are also prepared by themethod described in Example 17.

                                      TABLE 3                                     __________________________________________________________________________     ##STR81##                                                                    Example                                                                            Compound                  Melting                                        No.  No.   X.sup.1                                                                         X.sup.2                                                                         X.sup.3                                                                         R.sup.1  R.sup.2                                                                          Y point (°C.)                             __________________________________________________________________________    18   I-18  Cl                                                                              Cl                                                                              Cl                                                                              C(CH.sub.3).sub.3                                                                      H  N Oil                                            19   I-19  Cl                                                                              Cl                                                                              Cl                                                                               ##STR82##                                                                             H  N 63-65                                          20   I-20  Cl                                                                              Cl                                                                              Cl                                                                               ##STR83##                                                                             H  N Oil                                            __________________________________________________________________________

USE EXAMPLES EXAMPLE A Pyricularia Test (Rice)/Protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier,to the desired concentration.

To test for protective activity, young rice plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous sporesuspension of Pyricularia oryzae. The plants are then placed in agreenhouse at 100% relative atmospheric humidity and 25° C.

Evaluation of the disease infestation is carried out 4 days after theinoculation.

In this test, substances (I-1) and (I-3) according to the inventionexhibit a very good activity.

EXAMPLE B Pellicularia Test (Rice)

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier tothe desired concentration.

To test for activity, young rice plants in the 3 to 4 leaf stage aresprayed until dripping wet. The plants remain in a greenhouse until theyhave dried off. The plants are then inoculated with Pellicularia sasakiiand are placed at 25° C. and 100% relative atmospheric humidity.

The evaluation of the disease infestation is carried out 5 to 8 daysafter the inoculation.

In this test, substances (I-1) and (I-5) according to the inventionexhibit a very good activity.

EXAMPLE C Botrytis Test (Beans)/Protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, 2 small pieces of agar covered with Botrytiscinerea are placed on each leaf. The inoculated plants are placed in adarkened humid chamber at 20° C. 3 days after the inoculation, the sizeof the infected spots on the leaves is evaluated.

In this test, substance (I-1) according to the invention exhibits a verygood activity.

EXAMPLE D Erysiphe Test (Barley)/Protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are dusted with spores of Erysiphe graminisf.sp. hordei.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, substances (I-1) and (I-3) according to the inventionexhibit a very good activity.

EXAMPLE E Leptosphaeria nodorum Test (Wheat)/Protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a spore suspension ofLeptosphaeria nodorum. The plants remain for 48 hours in an incubationcabin at 20° C. and 100% relative atmospheric humidity.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of about 80%.

Evaluation is effected 10 days after the inoculation.

In this test, substances (I-1) and (I-3) according to the inventionexhibit a very good activity.

EXAMPLE F Pseudocercosporella herpotrichoides Test (Wheat)/Protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are inoculated at the base of the stem withspores of Pseudocercosporlla herpotrichoides.

The plants are then placed in a greenhouse at a temperature of about 10°C. and a relative atmospheric humidity of about 80%.

Evaluation is carried out 21 days after the inoculation.

In this test, substance (I-5) according to the invention exhibits a verygood activity.

The compounds shown below were employed as comparison substances in thefollowing use examples. ##STR84##

EXAMPLE G

To demonstrate the activity against fungi, the minimum inhibitoryconcentrations (MIC) of active compounds according to the invention aredetermined.

Active compounds according to the invention are added in concentrationsof 0.1 mg/l to 5,000 mg/l to an agar prepared from beer wort andpeptone. After the agar has solidified, it is contaminated with purecultures of the test organisms listed in the table. After storage at 28°C. and 60 to 70% relative atmospheric humidity for 2 weeks, the MIC isdetermined. The MIC is the lowest concentration of active compound atwhich there is no growth at all of the species of microbe used; it islisted in the following table G.

                                      TABLE G                                     __________________________________________________________________________    MIC's [mg/l] for the action of substances on fungi                            Test     Compounds according to the invention                                                                  Comparison substances                        organisms                                                                              I-3                                                                              I-1 I-16                                                                              I-17                                                                              I-18 I-12                                                                              (A)   (B)                                    __________________________________________________________________________    Alternaria tenius                                                                      35 50  35  500 100  20  >1000 >5000                                  Aspergillus niger                                                                      75 7.5 7.5  50 <20  5   >5000 5000                                   Aureobasidium-                                                                         35 5   7.5  50 10   5   1000  >5000                                  pullulans                                                                     Chaetomium                                                                             100                                                                              5   7.5 <20 <20  2    90   5000                                   globosum                                                                      Cladosporium                                                                           100                                                                              20  50  200 50   20  500   1000                                   cladosporioides                                                               Lentinus tigrinus                                                                      20 5   5    20 7.5  10  750    500                                   Penicillium                                                                            50 200     500 500  200 750   5000                                   glaucum                                                                       Sclerophoma                                                                            20 0.5 1    5  1    0.5                                              pityophila                                                                    Trichoderma                                                                            200                                                                              75  100 500 100  50                                               viride                                                                        __________________________________________________________________________

EXAMPLE H

Determination of the toxic limit values (kg/m³ of wood) of the activecompounds according to the invention for Coniophora puteana andPolyporus versicolor on pine and beech wood.

The toxic limit values are determined in accordance with the methoddescribed by H. P. Sutter, Int. Biodeterioration Bulletin 14 (3), 1978,pages 95 to 99.

For the tests, in each case freshly cut, thin pieces of cross-cut wood(size 40×40 mm, thickness about 2 mm) are impregnated with solutions ofvarious concentrations of the active compounds in vacuo, 15 wood samplesbeing impregnated with each solution of a particular concentration ofactive compound. Of these 15 samples 5 are in each case used for amycological test.

The amount of active compound absorbed is determined from the solventretention (which is determined by weighing the piece of wood before andafter the impregnation), the wood density and the concentration of theactive compound in the impregnating solution which remains.

Before the mycological test, the test specimens are sterilized withpropylene oxide and 1 test specimen each is introduced into a Petri dishin contact with the fully developed mycelium of test fungus on maltextract agar. After 6 weeks at 21° to 23° C., the toxicity limits areascertained visually.

The toxicity limits (kg/m³ of wood) for substances according to theinvention are shown in the following table; the toxicity limits indicatethe concentrations at which the wood is still just attacked (lower limitvalue) and at which the wood is no longer attacked (upper limit value).

                  TABLE H                                                         ______________________________________                                        Toxicity limits [kg/m.sup.3 of wood] of active compounds                      according to the invention for wood destructing fungi                         Active     Coniphora puteana                                                                          Polyporus versicolor                                  Compound   on pine wood on beech tree wood                                    ______________________________________                                        I-3        0.71-1.42    0.21-0.68                                             I-1        0.05-0.26    <0.02                                                 ______________________________________                                    

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswithin the spirit and scope of the invention will suggest themselves tothose skilled in the art.

What is claimed is:
 1. A halogenvinyl-azole derivative of the formula##STR85## in which R¹ represents phenyl, which can be substituted by oneto three identical or different substituents from the group consistingof halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenalkyl having1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms,halogenalkoxy having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenalkylthio having 1 or 2 carbon atoms and1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 7carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbon atomsin the alkoxy part, alkoximinoalkyl having 1 to 4 carbon atoms in thealkoxy part and 1 to 4 carbon atoms in the alkyl part, nitro andcyano,R² represents hydrogen, alkyl having 1 to 6 carbon atoms oralkenyl having 3 to 6 carbon atoms, X¹ represents fluorine, chlorine,bromine or iodine and x² represents fluorine, chlorine, bromine oriodine,or an addition product thereof with an acid or metal salt.
 2. Acompound or addition product thereof according to claim 1, in whichR¹represents phenyl which can be substituted by one to three identical ordifferent substituents from the group consisting of fluorine, chlorine,bromine, methyl, ethyl, tert.-butyl, methoxy, ethoxy, methylthio,trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, chlorofluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinoethyl, 1-methoximinoethyl, nitro and cyano,and R² represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butylor allyl.
 3. A compound according to claim 1, wherein such compound is1,2-dibromo-3-hydroxy-3-(4-chlorophenyl)-4-(1,3-imidazolyl)-1-butene ofthe formula ##STR86##
 4. A microbicidal composition comprising amicrobicidally effective amount of a compound or addition productaccording to claim 1 and an inert diluent.
 5. A method of combatingmicrobes in plant protection and in the preservation of materials, whichmethod comprises applying to such microbes or to their habitat amicrobicidally effective amount of a compound or addition productaccording to claim
 1. 6. A method of combating microbes in plantprotection and in the preservation of materials, which method comprisesapplying to such microbes or to their habitat a microbicidally effectiveamount of a compound or addition product according to claim 3.